Two-stage syngas production with separate char and product gas inputs into the second stage

ABSTRACT

A two-stage syngas production method to produce a final product gas from a carbonaceous material includes producing a first product gas in a first reactor, separating char from the first product gas to produce separated char and char-depleted product gas, and separately reacting the separated char and the char-depleted product gas with an oxygen-containing gas in a second reactor to produce a final product gas. The separated char is introduced into the second reactor above the char-depleted product gas. The solids separation device may include serially connected cyclones, and the separated char may be entrained in a motive fluid in an eductor to produce a char and motive fluid mixture prior to being transferred to the second reactor. A biorefinery method produces a purified product from the final product gas.

TECHNICAL FIELD

The present disclosure is directed to methods to produce product gasfrom carbonaceous materials using a two-step thermochemical process.

BACKGROUND

In recent years, there has been a shift towards innovative energy andenvironmental technologies to moderate climate change, reduce greenhousegas emissions, reduce air and water pollution, promote economicdevelopment, expand energy supply options, increase energy security,decrease dependence on imported oil, and strengthen rural economies.

One of these technologies entails conversion of a carbonaceous materialinto a product gas which can then be converted into liquid fuels,chemicals, renewable natural gas, hydrogen, hydrocarbons and otheruseful products. A product gas generation system is described whichincludes a first reactor, a solids separation device, and a secondreactor, and is configured to convert a carbonaceous material intoproduct gas. Carbonaceous material along with one or more gaseous orliquid reactants may be introduced into a pressurized reactor, or steamreformer, where they undergo one or more thermochemical reactions toproduce a product gas including char. Ideally, the carbonaceous materialis introduced into the reactor such that: feedstock throughput is high,the feedstock has high surface area to promote thermochemical reactions,the feedstock is distributed within the reactor, and the pressure of thereactor is maintained, even as the carbonaceous material is continuouslybeing introduced into the reactor.

Char may be separated from the product gas to produce a char-depletedproduct gas, and both the separated char and char-depleted product gasmay be introduced into a second reactor, or a char/hydrocarbon reformer.Within the second reactor, char is oxidized into carbon dioxide, carbonmonoxide, and other gases, and hydrocarbons present within thechar-depleted product gas are converted into additional product gasincluding hydrogen and carbon monoxide. Within the second reactor,reacting the oxygen-containing gas with the separated char to produce acombustion stream, and reacting the combustion stream with thechar-depleted product gas to produce a final product gas, the finalproduct gas having a reduced amount of char and a reduced amount ofhydrocarbons, relative to the char-depleted product gas. This simpletwo-step thermochemical process is new and has advantages in that isreduces capital intensity, reduces physical outlay of the gasifierisland of the integrated biorefinery, increases carbon intensity, andprovides for a simple, cost-effective installation.

An Integrated Biorefinery (IBR) is described and is configured toconvert a carbonaceous material into a useful intermediate and/orpurified product, wherein the IBR includes a feedstock preparationsystem, a feedstock delivery system, the product gas production system,a primary gas clean-up system, a compression system, a secondary gasclean-up system, a production system, and a purification or upgradingsystem. In embodiments, the IBR may include a two-stage gasifier islandand may be configured to produce and purify or upgrade products fromlarge quantities of carbonaceous materials including jet fuel, gasoline,diesel, alcohols such as ethanol, mixed alcohols, methanol, dimethylether, chemicals or chemical intermediates (plastics, solvents,adhesives, fatty acids, acetic acid, carbon black, olefins,oxochemicals, ammonia, etc.), Fischer-Tropsch products (LPG, Naphtha,Kerosene/diesel, lubricants, waxes), or synthetic natural gas.

In some instances, the product gas discharged from the second reactor,or the char/hydrocarbon reformer, may be converted into hydrogen,synthetic natural gas, or power. Processing of large quantities ofcarbonaceous materials requires having sufficient throughput in each ofa number of serially connected systems. The capacities of the varioussystems should be selected so that they collectively cooperate to meetup-time and fuel production requirements while also maximizing thereturn on investment (ROI).

SUMMARY

This Summary is provided merely to introduce certain concepts and not toidentify any key or essential features of the claimed subject matter.

-   Paragraph A. A method of producing a final product gas from a    carbonaceous material, comprising:-   in a first reactor, steam reforming the carbonaceous material to    produce a first product gas including char, hydrogen, carbon    monoxide, carbon dioxide, and hydrocarbons;-   in a solids separation device external to the first reactor,    separating the char from the first product gas to produce separated    char and char-depleted product gas, wherein the char-depleted    product gas has a reduced amount of char relative to the first    product gas;-   introducing into a second reactor, the separated char via a first    char input and the char-depleted product gas via a product gas input    distinct from the first char input;-   introducing an oxygen-containing gas into the second reactor; and-   in the second reactor, reacting the oxygen-containing gas with the    separated char and the char-depleted product gas to produce a final    product gas, the final product gas having a reduced amount of char    and a reduced amount of hydrocarbons, relative to the char-depleted    product gas;    -   wherein:-   along a vertical axis of the second reactor, the separated char is    introduced into the second reactor above the char-depleted product    gas.-   Paragraph B. The method according to Paragraph A, wherein the solids    separation device comprises serially connected first and second    cyclones; and the method comprises:-   passing the first product gas through both the first and second    cyclones to produce the char-depleted product gas, with the first    cyclone producing the separated char and the second cyclone    producing additional char; and-   introducing, into the second reactor, the separated char via the    first char input and the additional char via a second char input.-   Paragraph C. The method according to Paragraph B, comprising:-   introducing into the second reactor, both the separated char and the    additional char above the char-depleted product gas.-   Paragraph D. The method according to Paragraph A, wherein:-   the hydrocarbons in the first product gas include low molecular    weight hydrocarbons, aromatic hydrocarbons, and/or polyaromatic    hydrocarbons; and-   the low molecular weight hydrocarbons include one or more selected    from the group consisting of methane, ethane, ethylene, propane,    propylene, butane, and butene.-   Paragraph E. The method according to Paragraph A, comprising:-   introducing a fuel to the second reactor; and-   reacting the oxygen-containing gas with the fuel using a burner in    the second reactor.-   Paragraph F. The method according to Paragraph E, wherein:-   the fuel includes one or more selected from the group consisting of    tail-gas, Fischer-Tropsch tail-gas, natural gas, conditioned syngas,    propane, a methane-containing gas, naphtha, and off-gas from a    liquid fuel upgrading unit.-   Paragraph G. The method according to Paragraph A, comprising:-   entraining the separated char in a motive fluid to produce a char    and motive fluid mixture; and-   transferring the char and motive fluid mixture to the second    reactor;-   wherein: the motive fluid comprises one or more selected from the    group consisting of a gas, carbon dioxide, nitrogen, tail-gas,    conditioned syngas, syngas, off-gas from a downstream reactor,    steam, superheated steam, a vapor, and a superheated vapor.-   Paragraph H. The method according to Paragraph A, wherein:-   entraining the separated char in the motive fluid in an eductor to    produce the char and motive fluid mixture.-   Paragraph I. The method according to Paragraph A, comprising, in the    first reactor:-   indirectly heating particulate heat transfer material in the first    reactor with a plurality of pulse combustion heat exchangers; and-   introducing superheated steam and the carbonaceous material into the    first reactor to steam reform the carbonaceous material.-   Paragraph J. The method according to Paragraph I, comprising:-   also introducing an oxygen-containing gas into the first reactor to    promote partial oxidation of the carbonaceous material to produce    carbon monoxide and carbon dioxide.-   Paragraph K. The method according to Paragraph A, wherein:-   introducing additional oxygen-containing gas into the second reactor    between the first char input and the product gas input along the    vertical axis to promote partial oxidation of the char-depleted    product gas, wherein the additional oxygen-containing gas.-   Paragraph L. A method to produce a purified product from    carbonaceous material, comprising:-   producing a final product gas from the carbonaceous material    according to Paragraph A after introducing the carbonaceous material    into the first reactor from a feedstock delivery system;-   in a primary gas clean-up system, cooling and removing solids and    water vapor from the final product gas to produce a first cleaned    product gas;-   in a compression system, compressing the first cleaned product gas    to produce a compressed product gas;-   in a secondary gas clean-up system, removing contaminants and carbon    dioxide from the compressed product gas to produce a second cleaned    product gas and a carbon dioxide-rich stream;-   in a production system, producing an intermediate product from at    least a portion of the second cleaned product gas, the intermediate    product includes one or more selected from the group consisting of    liquid fuel, a chemical, ethanol, mixed alcohols, methanol, dimethyl    ether, Fischer-Tropsch products, and synthetic natural gas; and-   in a purification system, purifying or upgrading the intermediate    product to produce a purified product, wherein the purification    system includes one or more selected from the group consisting of    isomerization, hydrotreating, hydrocracking, distillation, and    adsorption.-   Paragraph M. The method according to Paragraph L, comprising:-   recycling and mixing at least a portion of the carbon dioxide-rich    stream removed in the secondary gas clean-up system with the char    produced in Paragraph A to produce a mixture of char and carbon    dioxide, and transferring the mixture of char and carbon dioxide to    the first char input of the second reactor.-   Paragraph N. The method according to Paragraph L, wherein:-   in the production system, producing tail gas, and recycling and    mixing at least a portion of the tail gas with the char produced in    Paragraph A to produce a mixture of char and gas, and transferring    the mixture of char and tail gas to the first char input of the    second reactor.-   Paragraph O. The method according to Paragraph L, wherein:-   in the production system, producing tail-gas, and introducing at    least a portion of the tail-gas to the second reactor, and reacting    the tail-gas with the oxygen-containing gas prior to reaction with    the char and/or the char-depleted product gas.-   Paragraph P. The method according to Paragraph L, wherein:-   in the purification system, producing an off-gas stream, and    recycling and mixing at least a portion of the off-gas stream with    the char produced in claim 1 to produce a mixture of char and gas,    and transferring the mixture of mixture of char and gas to the first    char input of the second reactor; and/or-   in the purification system, producing off-gas stream, and    introducing at least a portion of the off-gas stream to the second    reactor, and reacting the off-gas stream with the oxygen-containing    gas prior to reaction with the char and/or the char-depleted product    gas.-   Paragraph Q. The method according to Paragraph L, wherein:-   the first reactor comprises a cylindrical, up-flow,    refractory-lined, steel pressure vessel including a fluidized bed;    and-   the second reactor comprises a cylindrical, down-flow,    non-catalytic, refractory-lined, steel pressure vessel.-   Paragraph R. The method according to Paragraph L, wherein:    -   the carbonaceous material includes municipal solid waste; and    -   in a feedstock preparation system, processing the municipal        solid waste to produce sorted municipal solid waste in at least        one processing step, including one or more processing steps        selected from the group consisting of large objects removal,        recyclables removal, ferrous metal removal, size reduction,        drying or water removal, biowaste removal, non-ferrous metal        removal, polyvinyl chloride removal, glass removal, size        reduction and pathogen removal; and    -   introducing the sorted municipal solid waste to the feedstock        delivery system.-   Paragraph S. The method according to Paragraph L, wherein:-   in the production system, producing the intermediate product from at    least a portion of the second cleaned product gas within one or more    reactors selected from the group consisting of a multi-tubular    reactor, a multi-tubular fixed-bed reactor, an entrained flow    reactor, a slurry reactor, a fluid bed reactor, a circulating    catalyst reactor, a riser reactor, a can reactor, a microchannel    reactor, a fixed bed reactor, a bioreactor and a moving bed reactor.-   Paragraph T. The method according to Paragraph S, wherein:-   the reactor includes one or more bioreactors selected from the group    consisting of a continuous stirred tank bioreactor, a bubble column    bioreactor, a microbubble reactor, an airlift bioreactor, a    fluidized bed bioreactor, a packed bed bioreactor and a    photo-bioreactor.-   Paragraph U. The method according to Paragraph T, wherein:-   the bioreactor includes genetically modified organisms which undergo    anaerobic respiration.-   Paragraph V. A biorefinery system configured to produce a purified    product from carbonaceous material, the system includes:    -   a feedstock delivery system configured to accept and transfer a        source of carbonaceous material to a first reactor, wherein the        feedstock delivery system includes one or more systems selected        from the group consisting of a plug feeder system, a        densification system, a lock-hopper system, a screw auger, and a        solids transport conduit;    -   the first reactor configured to steam reform the carbonaceous        material to produce a first product gas including char,        hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons;    -   a solids separation device configured to accept the first        product gas and separate the char therefrom to produce separated        char and char-depleted product gas, wherein the char-depleted        product gas has a reduced amount of char relative to the first        product gas;    -   a second reactor having a vertical axis and configured to accept        both the separated char via a first char input and the        char-depleted product gas via a product gas input, the first        char input being at a higher elevation along the vertical axis        than the product gas input, the second reactor configured to        react the oxygen-containing gas with the separated char and the        char-depleted product gas to produce a final product gas, the        final product gas having a reduced amount of char and a reduced        amount of hydrocarbons, relative to the char-depleted product        gas;    -   a primary gas clean-up system configured to cool and removing        solids and water vapor from the final product gas to produce a        first cleaned product gas;    -   a compression system configured to compress the first cleaned        product gas to produce a compressed product gas;    -   a secondary gas clean-up system configured to remove        contaminants and carbon dioxide from the compressed product gas        to produce a second cleaned product gas and a carbon        dioxide-rich stream;    -   a production system configured to produce an intermediate        product from at least a portion of the second cleaned product        gas, the intermediate product includes one or more selected from        the group consisting of liquid fuel, a chemical, ethanol, mixed        alcohols, methanol, dimethyl ether, Fischer-Tropsch products,        and synthetic natural gas; and    -   a purification system configured to purify the intermediate        product to produce a purified product, wherein the purification        system includes one or more selected from the group consisting        of isomerization, hydrotreating, hydrocracking, distillation,        and adsorption.-   Paragraph W. The biorefinery system according to Paragraph V,    wherein:-   the second reactor includes a burner configured to react the    oxygen-containing gas with a fuel.-   Paragraph X. The biorefinery system according to Paragraph V,    wherein:-   the first reactor comprises a cylindrical, up-flow,    refractory-lined, steel pressure vessel including a fluidized bed;    and-   the second reactor comprises a cylindrical, down-flow,    non-catalytic, refractory-lined, steel pressure vessel.-   Paragraph Y. The biorefinery system according to Paragraph V,    further comprising:-   an eductor configured to receive and entrain the separated char in a    motive fluid, prior to introducing the char into the second reactor.-   Paragraph Z. The biorefinery system according to Paragraph V,    wherein:-   the solids separation device comprises serially connected first and    second cyclones through which the first product gas passes to remove    char.-   Paragraph AA. The biorefinery system according to Paragraph V,    comprising:-   a feedstock preparation system configured to accept a source of    carbonaceous material comprising municipal solid waste and produce    sorted municipal solid waste in at least one processing step,    including one or more processing steps selected from the group    consisting of large objects removal, recyclables removal, ferrous    metal removal, size reduction, drying or water removal, biowaste    removal, non-ferrous metal removal, polyvinyl chloride removal,    glass removal, size reduction, and pathogen removal; and-   the feedstock delivery system is configured to accept the sorted    municipal solid waste from the feedstock preparation system as the    source of carbonaceous material.-   Paragraph AB. The biorefinery system according to Paragraph V,    wherein:-   the production system includes a reactor, the reactor includes one    or more reactors selected from the group consisting of a    multi-tubular reactor, a multi-tubular fixed-bed reactor, an    entrained flow reactor, a slurry reactor, a fluid bed reactor, a    circulating catalyst reactor, a riser reactor, a can reactor, a    microchannel reactor, a fixed bed reactor, a bioreactor, and a    moving bed reactor.-   Paragraph AC. The biorefinery system according to Paragraph V,    wherein:-   the production system comprises bioreactor including one or more    selected from the group consisting of a continuous stirred tank    bioreactor, a bubble column bioreactor, a microbubble reactor, an    airlift bioreactor, a fluidized bed bioreactor, a packed bed    bioreactor, and a photo-bioreactor.-   Paragraph AD. The biorefinery system according to Paragraph V,    wherein:-   the production system comprises bioreactor including one or more    selected from the group consisting of a continuous stirred tank    bioreactor, a bubble column bioreactor, a microbubble reactor, an    airlift bioreactor, a fluidized bed bioreactor, a packed bed    bioreactor, and a photo-bioreactor.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying figures show schematic process flowcharts of preferredembodiments and variations thereof. A full and enabling disclosure ofthe content of the accompanying claims, including the best mode thereofto one of ordinary skill in the art, is set forth more particularly inthe remainder of the specification, including reference to theaccompanying figures showing how the preferred embodiments and othernon-limiting variations of other embodiments described herein may becarried out in practice, in which:

FIG. 1 shows a simplistic block flow diagram of one embodiment of aproduct gas production system (1000).

FIG. 2 shows a simplistic block flow diagram of one embodiment of aproduct gas production system (1000) including: a first reactor (100)configured to produce a first product gas (122) including char, a solidsseparation device (150) configured to separate the char from the firstproduct gas (122) to produce separated char (144) and char-depletedproduct gas (126), and a second reactor (200) configured to separatelyaccept both the separated char (144) and the char-depleted product gas(126), wherein the separated char (144) is introduced to the secondreactor at a first elevation (EL1) and the char-depleted product gas(126) at a second elevation (EL2), wherein the first elevation is higherthan the second elevation along a vertical axis (AX2) of the secondreactor (200).

FIG. 2A shows a simplistic diagram of another embodiment of a productgas production system (1000) including: a first reactor (100) configuredto produce a first product gas (122) including char, a first solidsseparation device (150) configured to separate the char from the firstproduct gas (122) to produce separated char (144) and a firstchar-depleted product gas (126), a second solids separation device(150′) configured to separate additional char from the firstchar-depleted product gas (126) to produce additional separated char(144′) and a second char-depleted product gas (126′), and a secondreactor (200) configured to separately accept both streams of separatedchar (144, 144′) and the second char-depleted product gas (126′),wherein both streams of separated char (144, 144′) are introduced to thesecond reactor (200) at two first elevations (ELL ELF) and the secondchar-depleted product gas (126′) is also introduced at a secondelevation (EL2), wherein both of the first elevations (ELL ELF) arelocated higher than the second elevation (EL2) along a vertical axis(AX2) of the second reactor (200).

FIG. 3 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (3-1), a first annular port (3-2), a second annular port (3-3), anda third annular port (3-4).

FIG. 4 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (4-1), a first annular port (4-2), and a second annular port (4-3).

FIG. 5 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (5-1), a first annular port (5-2), and a second annular port (5-3).

FIG. 6 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (6-1) and a first annular port (6-2).

FIG. 7 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes a pulsecombustor.

FIG. 8 shows another simplistic representation of a burner (246)connected to the second reactor (200), wherein the burner (246) includesa pulse combustor.

FIG. 9 shows a simplistic diagram of one embodiment of IntegratedBiorefinery (IBR) including the product gas production system (1000) asdisclosed in FIGS. 1, 2 and 2A.

DETAILED DESCRIPTION Notation and Nomenclature

Before the disclosed systems and processes are described, it is to beunderstood that the aspects described herein are not limited to specificembodiments, apparatus, or configurations, and as such can, of course,vary. It is also to be understood that the terminology used herein isfor the purpose of describing particular aspects only and, unlessspecifically defined herein, is not intended to be limiting.

As used herein the term “carbonaceous material” refers to a solid orliquid substance that contains carbon such as for instance, agriculturalresidues, agro-industrial residues, animal waste, biomass, cardboard,coal, coke, energy crops, farm slurries, fishery waste, food waste,fruit processing waste, lignite, municipal solid waste (MSW), paper,paper mill residues, paper mill sludge, paper mill spent liquors,plastics, refuse derived fuel (RDF), sewage sludge, tires, urban waste,wood products, wood wastes and a variety of others. All carbonaceousmaterials contain both “fixed carbon components” and “volatilecomponents”, such as for example woody biomass, MSW, or RDF.

As used herein the term “char” refers to a carbon-containing solidresidue derived from a carbonaceous material and is comprised of the“fixed carbon components” of a carbonaceous material. Char includescarbon and ash.

As used herein the term “product gas” refers to syngas or flue gasdischarged from a thermochemical reactor undergoing thermochemicalprocesses including pyrolysis, steam reforming, partial oxidation, dryreforming, or combustion.

As used herein the term “syngas” refers to a mixture of carbon monoxide(CO), hydrogen (H₂), and other vapors/gases, also including char, if anyand usually produced when a carbonaceous material reacts with steam(H₂O), carbon dioxide (CO₂) and/or oxygen (O₂). While steam is thereactant in steam reforming, CO₂ is the reactant in dry reforming.Generally, for operation at a specified temperature, the kinetics ofsteam reforming is faster than that of dry reforming and so steamreforming tends to be favored and more prevalent. Syngas might alsoinclude low molecular weight hydrocarbons (like methane, ethane,ethylene, propane, propylene, butane, butene, etc.), aromatichydrocarbons such as volatile organic compounds (VOC) and/orsemi-volatile organic compounds (SVOC).

As used herein the term “volatile organic compounds” or acronym “(VOC)”or “VOC” refer to aromatic hydrocarbons including benzene, toluene,phenol, styrene, xylene, and cresol.

As used herein the term “semi-volatile organic compounds” or acronym“(SVOC)” or “SVOC” refer to polyaromatic hydrocarbons, such as indene,indane, naphthalene, methylnaphthalene, acenaphthylene, acenaphthalene,anthracene, phenanthrene, (methyl-) anthracenes/phenanthrenes,pyrene/fluoranthene, methylpyrenes/benzofluorenes, chrysene,benz[a]anthracene, methylchrysenes, methylbenz[a]anthracenes, perylene,benzo[a]pyrene, dibenz[a,kl]anthracene, and dibenz[a,h]anthracene.

As used herein the term “oxygen-containing gas” refers to air,oxygen-enriched-air i.e. greater than 21 mole % O₂, or substantiallypure oxygen, i.e. greater than about 95 mole % oxygen (the remainderusually comprising N₂ and/or rare gases). In embodiments, an airseparation unit (ASU) is used to produce a source of “oxygen-containinggas” from air. In embodiments, a plurality of air separation unit (ASU)are used to produce a source of “oxygen-containing gas” from air.

In embodiments, the air separation unit (ASU) includes a fractionaldistillation unit. In embodiments, the air separation unit (ASU)includes a plurality of fractional distillation units. In embodiments,the air separation unit (ASU) includes a cryogenic air separation unit.In embodiments, the air separation unit (ASU) includes a plurality ofcryogenic air separation units. In embodiments, the air separation unit(ASU) includes a membrane or a plurality of membranes. In embodiments,the air separation unit (ASU) includes a pressure swing adsorption (PSA)unit. In embodiments, the air separation unit (ASU) includes a pluralityof pressure swing adsorption (PSA) units. In embodiments, the airseparation unit (ASU) includes a vacuum pressure swing adsorption (VPSA)unit. In embodiments, the air separation unit (ASU) includes a pluralityof vacuum pressure swing adsorption (VPSA) units. In embodiments, theair separation unit (ASU) includes one or more selected from the groupconsisting of a fractional distillation unit, cryogenic air separationunit, a membrane, a pressure swing adsorption (PSA) unit, a vacuumpressure swing adsorption (VPSA) unit. In embodiments, the airseparation unit (ASU) includes two or more selected from the groupconsisting of a fractional distillation unit, cryogenic air separationunit, a membrane, a pressure swing adsorption (PSA) unit, a vacuumpressure swing adsorption (VPSA) unit.

As used herein the term “flue gas” refers to a vapor or gaseous mixturecontaining varying amounts of nitrogen (N₂), carbon dioxide (CO₂), water(H₂O), and oxygen (O₂). Flue gas is generated from the thermochemicalprocess of combustion.

As used herein the term “thermochemical process” refers to a broadclassification including various processes that can convert acarbonaceous material into product gas. Among the numerousthermochemical processes or systems that can be considered for theconversion of a carbonaceous material, the present disclosurecontemplates: pyrolysis, steam reforming, partial oxidation, dryreforming, and/or combustion. Thermochemical processes may be eitherendothermic or exothermic in nature depending upon the specific set ofprocessing conditions employed. Stoichiometry and composition of thereactants, type of reactants, reactor temperature and pressure, heatingrate of the carbonaceous material, residence time, carbonaceous materialproperties, and catalyst or bed additives all dictate what subclassification of thermochemical processing the system exhibits.

As used herein the term “thermochemical reactor” refers to a reactor(e.g., a first reactor, a second reactor) that accepts a carbonaceousmaterial, char, low molecular weight hydrocarbons, VOC, SVOC, or productgas and converts it into one or more product gases.

Pyrolysis Reaction:

As used herein the term “pyrolysis” is the endothermic thermaldegradation reaction that organic material goes through in itsconversion into a more reactive liquid/vapor/gas state.Carbonaceous material+heat→VOC+SVOC+H₂O+CO+CO₂+H₂+CH₄+low molecularweight hydrocarbons+charSteam Reforming Reactions:

As used herein the term “steam reforming” refers to a thermochemicalprocess where steam reacts with a carbonaceous material to yield syngas.The main reaction is endothermic (consumes heat) wherein the operatingtemperature range is between 570° C. and 900° C. (1,058° F. and 1,652°F.), depending upon the chemistry of the carbonaceous material.H₂O+C+Heat→H₂+COWater Gas Shift Reaction:

As used herein the term “water-gas shift” refers to a thermochemicalprocess comprising a specific chemical reaction that occurssimultaneously with the steam reforming reaction to yield hydrogen andcarbon dioxide. The main reaction is exothermic (releases heat) whereinthe operating temperature range is between 570° C. and 900° C. (1,058°F. and 1,652° F.), depending upon the chemistry of the carbonaceousmaterial.H₂O+CO→H₂+CO₂+HeatDry Reforming Reaction:

As used herein the term “dry reforming” refers to a thermochemicalprocess comprising a specific chemical reaction where carbon dioxide isused to convert a carbonaceous material into carbon monoxide. Thereaction is endothermic (consumes heat) wherein the operatingtemperature range is between 600° C. and 1,000° C. (1,112° F. and 1,832°F.), depending upon the chemistry of the carbonaceous material.CO₂+C+Heat→2COPartial Oxidation Reaction:

As used herein the term “partial oxidation” refers to a thermochemicalprocess wherein sub-stoichiometric oxidation of a carbonaceous materialtakes place to exothermically produce carbon monoxide, carbon dioxideand/or water vapor. The reactions are exothermic (release heat) whereinthe operating temperature range is between 500° C. and 1,700° C. (932°F. and 3,092° F.), depending upon the chemistry of the carbonaceousmaterial. Oxygen reacts exothermically (releases heat): 1) with thecarbonaceous material to produce carbon monoxide and carbon dioxide; 2)with hydrogen to produce water vapor; and 3) with carbon monoxide toproduce carbon dioxide.4C+3O₂→CO+CO₂+HeatC+½O₂→CO+HeatH₂+½O₂→H₂O+HeatCO+½O₂→CO₂+HeatCombustion Reaction:

As used herein the term “combustion” refers to an exothermic (releasesheat) thermochemical process wherein at least the stoichiometricoxidation of a carbonaceous material takes place to generate flue gas.C+O₂→CO₂+HeatCH₄+O₂→CO₂+2H₂O+Heat

Some of these reactions are fast and tend to approach chemicalequilibrium while others are slow and remain far from reachingequilibrium. The composition of the product gas will depend upon bothquantitative and qualitative factors. Some are unit specific i.e.reactor size/scale specific and others are carbonaceous materialfeedstock specific. The quantitative parameters are: carbonaceousmaterial properties, carbonaceous material injection flux, reactoroperating temperature, pressure, gas and solids residence times,carbonaceous material heating rate, fluidization medium and fluidizationflux; the qualitative factors are: degree of bed mixing and gas/solidcontact, and uniformity of fluidization and carbonaceous materialinjection.

Reference will now be made in detail to various embodiments of thedisclosure. Each embodiment is provided by way of explanation of thedisclosure, not limitation of the disclosure. In fact, it will beapparent to those skilled in the art that modifications and variationscan be made in the disclosure without departing from the teaching andscope thereof. For instance, features illustrated or described as partof one embodiment to yield a still further embodiment derived from theteaching of the disclosure. Thus, it is intended that the disclosure orcontent of the claims cover such derivative modifications and variationsto come within the scope of the disclosure or claimed embodimentsdescribed herein and their equivalents.

Additional objects and advantages of the disclosure will be set forth inpart in the description which follows, and in part will be obvious fromthe description, or may be learned by practice of the claims. Theobjects and advantages of the disclosure will be attained by means ofthe instrumentalities and combinations and variations particularlypointed out in the appended claims.

FIG. 1:

FIG. 1 shows a simplistic diagram of one embodiment of a product gasproduction system (1000). The product gas production system (1000) ofFIG. 1 includes a first reactor (100), a solids separation device (150),and a second reactor (200).

In embodiments, the first reactor (100) includes a first interior (101)and has a first vertical axis (AX1). In embodiments, the second reactor(200) includes a second interior (201) and has a second vertical axis(AX2). The first reactor (100) generates a first product gas (122) byreacting a source of carbonaceous material (102) with a reactant (106),such as superheated steam, in a steam reforming reaction, wherein thefirst product gas (122) includes syngas comprising hydrogen, carbonmonoxide, carbon dioxide, low molecular weight hydrocarbons, volatileorganic compounds, semi-volatile organic compounds, and char. Inembodiments, the second reactor includes a char/hydrocarbon reformer.

A particulate heat transfer material (105) is contained within theinterior (101) of the first reactor (100) and is configured to providecontact with the carbonaceous material (102) and a reactant (106), suchas steam, superheated steam, and optionally carbon dioxide (recycledfrom downstream secondary gas clean-up section of the IntegratedBiorefinery (IBR) as shown in FIG. 9). In embodiments, the product gasproduction system (1000) is included inside of an Integrated Biorefinery(IBR).

In embodiments, the particulate heat transfer material (105) iscomprised of alumina, zirconia, sand, olivine sand, limestone, dolomite,or catalytic materials, any of which may be hollow in form, such asmicroballoons or microspheres. In embodiments, a first oxygen-containinggas (118) is provided to the interior (101) of the first reactor (100)to react with the carbonaceous material (102). In embodiments, a sourceof carbon dioxide is provided to the first reactor (100) together withthe source of carbonaceous material (102), wherein the carbonaceousmaterial (102) includes a mixture of carbonaceous material and carbondioxide. In embodiments, the particulate heat transfer material (105)enhances mixing, heat and mass transfer, and reaction between thecarbonaceous material (102), reactant (106), and the firstoxygen-containing gas (118) within the interior (101) for the firstreactor (100).

The first product gas (122) is discharged from the first reactor (100)via a first product gas output (124) and is routed towards a solidsseparation device (150) which separates the char (144) from the firstproduct gas (122) to produce separated char (144) and char-depletedproduct gas (126). The char-depleted product gas (126) has a reducedamount of char (144) within it relative to the first product gas (122).

The solids separation device (150) accepts the first product gas (122)via a first separation input (152). The solids separation device (150)accepts the first product gas (122) from the first product gas output(124) of the first reactor (100). The solids separation device (150)includes any conceivable means to separate solid char from the firstproduct gas, and preferably includes a cyclone, a filter, or aseparator. The char-depleted product gas (126) is discharged from thesolids separation device (150) via the first separation gas output(156). The separated char (144) is discharged from the solids separationdevice (150) via the first separation char output (154).

The second reactor (200) is configured to accept both the separated char(144) and the char-depleted product gas (126) discharged from the solidsseparation device (150). The separated char (144) is introduced to theinterior (201) of the second reactor (200) via a first char input (204).The char-depleted product gas (126) is introduced to the interior (201)of the second reactor (200) via a product gas input (206).

In embodiments, the first char input (204) is positioned at a firstelevation (EL1) along the second vertical axis (AX2) of the secondreactor (200). In embodiments, the product gas input (206) is positionedat a second elevation (EL2) along the second vertical axis (AX2) of thesecond reactor (200). In embodiments, the first char input (204) at thefirst elevation (EL1) is higher than the second elevation (EL2) of theproduct gas input (206). In embodiments, the separated char (144) isintroduced to the interior (201) of the second reactor (200) at anelevation higher than where the product gas input (206) is introduced tothe interior (201) of the second reactor (200).

The separated char (144) and the char-depleted product gas (126) areboth reacted within the interior (201) of the second reactor (200) toproduce a second reactor product gas (222). The second reactor productgas (222) is discharged from the second reactor (200) via a secondproduct gas output (224). In embodiments, the second reactor product gas(222) is a final product gas resulting from this new two-stepthermochemical process. The separated char (144) is reacted with asecond oxygen-containing gas (218) within the interior (201) of thesecond reactor (200) to produce carbon monoxide and/or carbon dioxide.The char-depleted product gas (126) is reacted with a secondoxygen-containing gas (218) and the products of the char reaction withinthe interior (201) of the second reactor (200) to produce additionalproduct gas, or additional syngas, not only including hydrogen, carbonmonoxide, and carbon dioxide. The char-depleted product gas (126) isreacted with a second oxygen-containing gas (218) within the interior(201) of the second reactor (200) to produce an improved syngas having ahigher concentration of carbon monoxide and hydrogen, relative to thatfound in the char-depleted product gas (126).

FIG. 2:

FIG. 2 shows a simplistic diagram of one embodiment of a product gasproduction system (1000) including: a first reactor (100) configured toproduce a first product gas (122) including char, a solids separationdevice (150) configured to separate the char from the first product gas(122) to produce separated char (144) and char-depleted product gas(126), and second reactor (200) configured to separately accept both theseparated char (144) and the char-depleted product gas (126), whereinthe separated char (144) is introduced to the second reactor at a firstelevation (EL1) and the char-depleted product gas (126) at a secondelevation (EL2), wherein the first elevation is higher than the secondelevation along a vertical axis (AX2) of the second reactor (200).

The product gas production system (1000) of FIG. 2 includes a moredetailed view of the first reactor (100), a solids separation device(150), and a second reactor (200) as depicted in FIG. 1. In embodiments,the first reactor (100) includes a first interior (101) and has a firstvertical axis (AX1). In embodiments, the second reactor (200) includes asecond interior (201) and has a second vertical axis (AX2).

FIG. 2 shows a carbonaceous material (102) being introduced to theinterior (101) of the first reactor (100) via an input (104). In thefirst reactor (100) the source of carbonaceous material (102) is steamreformed, via a steam reforming reaction, to produce the first productgas (122) including syngas comprising hydrogen, carbon monoxide, carbondioxide, low molecular weight hydrocarbons, volatile organic compounds,semi-volatile organic compounds, and char.

A particulate heat transfer material (105) is contained within theinterior (101) first reactor (100) and is configured to provide contactwith the carbonaceous material (102) and a reactant (106), such assteam, superheated steam, and optionally carbon dioxide (recycled fromdownstream secondary gas clean-up section of the Integrated Biorefinery(IBR) as shown in FIG. 9).

A first reactor heat exchanger (HX-1) is immersed beneath a fluid bedlevel (L-1) of the particulate heat transfer material (105). The firstreactor heat exchanger (HX-1) may include a plurality of heatexchangers, such as pulse combustion heat exchangers. Any type of heatexchanger may be used, such as pulse heater tailpipes, electrical heaterrods in thermowells, fuel cells, heat pipes, fire-tubes, annulus-typeheat exchangers, or radiant tubes.

In embodiments, the first reactor heat exchanger (HX-1) may be a pulsecombustion heat exchanger that combusts a source of fuel (110) to form apulse combustion stream (114) comprising flue gas. The pulse combustionstream (114) indirectly heats the particulate heat transfer material(105) of the first reactor (100). As used herein, indirectly heating theparticulate heat transfer material (105) means that the pulse combustionstream (114) does not contact the contents of the particulate heattransfer material (105) within the first reactor (100). In other words,the pulse combustion stream (114) indirectly heats the particulate heattransfer material (105) which in turn directly contacts the carbonaceousmaterial (102), reactant (106), and the first oxygen-containing gas(118) within the interior (101) of the first reactor (100). Inembodiments, the fuel for the plurality of pulse combustion heatexchangers includes one or more selected from the group consisting ofconditioned syngas, tail-gas, Fischer Tropsch tail-gas, naphtha,off-gases from a downstream liquid fuel production system, natural gas,steam-diluted natural gas, propane, hydrocarbons, and hydrocarbonmixtures.

In embodiments, the particulate heat transfer material (105) iscomprised of alumina, zirconia, sand, olivine sand, limestone, dolomite,or catalytic materials, any of which may be hollow in form, such asmicroballoons or microspheres. In embodiments, the particulate heattransfer material (105) enhances mixing, heat and mass transfer, andreaction between the carbonaceous material (102), reactant (106), andthe first oxygen-containing gas (118). In embodiments, the first reactorincludes a steam reformer. In embodiments, the first reactor includes anindirectly heated steam reformer.

In embodiments, a first oxygen-containing gas (118) is provided to theinterior (101) of the first reactor (100) via a first oxygen-containinggas input (120) to react with the carbonaceous material (102). Inembodiments, a reactant (106), such as steam, or superheated steam, avapor, or a superheated vapor, is provided to the interior (101) of thefirst reactor (100) via a reactant input (108) to react with thecarbonaceous material (102). In embodiments, the first oxygen-containinggas input (120) and the reactant input (108) are not separate inputs tothe first reactor (100), and are introduced to the first reactor (100)as a mixture of the reactant (106) and the first oxygen-containing gas(118), and are introduced to the interior (101) of the first reactor(100) through a fluidization distributor (121) to fluidize particulateheat transfer (105) included therein, as shown in FIG. 2. Inembodiments, the first oxygen-containing gas input (120) and thereactant input (108) are separate inputs to the first reactor (100).

FIG. 2 shows a first reactor (100) having a first interior (101)provided with a freeboard zone (FB-1) located above the fluid bed level(L-1) of the particulate heat transfer material (105). In embodiments,an internal cyclone (125) is positioned within the freeboard zone (FB-1)of the first reactor (100). The internal cyclone (125) is configured toseparate particulate heat transfer material (105) from, product gaswithin the freeboard zone (FB-1) of the first reactor (100) and returnthe particulate heat transfer material (105) back to below the fluid bedlevel (L-1) while permitting the product gas to leave the interior (101)of the first reactor (100) en route to the solids separation device(150).

The first product gas (122) is discharged from the first reactor (100)via a first product gas output (124) and is routed towards a solidsseparation device (150) which separates the char (144) from the firstproduct gas (122) to produce separated char (144) and a char-depletedproduct gas (126), wherein the char-depleted product gas (126) has areduced amount of char (144) within it relative to the first product gas(122).

The solids separation device (150) accepts the first product gas (122)via a first separation input (152). The solids separation device (150)accepts the first product gas (122) from the first product gas output(124) of the first reactor (100). The solids separation device (150)includes any conceivable means to separate solid char from the firstproduct gas, and preferably includes a cyclone, a filter, or aseparator. The char-depleted product gas (126) is discharged from thesolids separation device (150) via the first separation gas output(156). The separated char (144) is discharged from the solids separationdevice (150) via the first separation char output (154).

In embodiments, a source of motive fluid (149), such as carbon dioxide,a gas such as conditioned syngas or tail-gas or off-gas from adownstream reactor, steam, superheated steam, a vapor, a superheatedvapor, is mixed with the separated char (144) for transporting theseparated char (144) to the first char input (204) of the second reactor(200). In embodiments, the motive fluid with mixed with or entrains theseparated char to produce a char and motive fluid mixture, and thentransferring the char and motive fluid mixture to the second reactor forreaction with an oxygen-containing gas, wherein: the motive fluidcomprises one or more selected from the group consisting of a gas,carbon dioxide, nitrogen, tail-gas, conditioned syngas, syngas, off-gasfrom a downstream reactor, steam, superheated steam, a vapor, and asuperheated vapor.

In embodiments, an eductor (148) is used to mix and transport the motivefluid (149) with the separated char (144) to be transferred to the firstchar input (204) of the second reactor (200). In embodiments, theeductor (148) may include a venturi eductor and/or a venturi transportsystem for dilute phase pneumatic conveying of the char (144) into thesecond reactor (200) with the motive fluid (148). In embodiments, theeductor (148) includes a Solids Handling Eductor provided by Schutte &Koerting located at 2510 Metropolitan Drive, Trevose, Pa. 19053(www.s-k.com).

The second reactor (200) is configured to accept both the separated char(144) and the char-depleted product gas (126) discharged from the solidsseparation device (150). The separated char (144) is introduced to theinterior (201) of the second reactor (200) via a first char input (204).The char-depleted product gas (126) is introduced to the interior (201)of the second reactor (200) via a product gas input (206). The solidsseparation device (150) separates the char from the first product gas(122) to provide two separate streams, the separated char (144) and thechar-depleted product gas (126), which are then separately introduced tothe interior (201) of the second reactor (201) at two different reactionzones. The kinetics of reacting the separated char (144) into additionalproduct gas are much slower than reacting char-depleted product gas(126) into additional product gas. This difference in reaction kineticsis the main reason for first introducing the separated char (144) into ahigher region of the second reactor (200) followed by secondlyintroducing the char-depleted product gas (126) into a relatively lowerregion of the second reactor (200).

In embodiments, the first char input (204) is positioned at a firstelevation (EL1) along the second vertical axis (AX2) of the secondreactor (200). In embodiments, the product gas input (206) is positionedat a second elevation (EL2) along the second vertical axis (AX2) of thesecond reactor (200). In embodiments, the first char input (204) at thefirst elevation (EL1) is higher than the second elevation (EL2) of theproduct gas input (206). In embodiments, the first char input (204) ishigher than the product gas input (206) along the second vertical axis(AX2) of the second reactor (200). In embodiments, the separated char(144) is introduced to the interior (201) of the second reactor (200) atan elevation higher than where the product gas input (206) is introducedto the interior (201) of the second reactor (200). The separated char(144) and the char-depleted product gas (126) are both reacted withinthe interior (201) of the second reactor (200) to produce a secondreactor product gas (222).

In embodiments, a second reactor heat exchanger (HX-2) is in thermalcontact with the interior (201) of the second reactor (200). Inembodiments, the second reactor heat exchanger (HX-2) may include aradiant syngas cooler. In embodiments, the second reactor heat exchanger(HX-2) may include radiant syngas cooler with a double shell design or amembrane wall. In embodiments, the second reactor heat exchanger (HX-2)is configured to remove heat from within the interior (201) of thesecond reactor (200) by use of a heat transfer medium (210). Inembodiments, the heat transfer medium (210) enters the second reactorheat exchanger (HX-2) via a heat transfer medium inlet (212) and exitsvia a heat transfer medium outlet (216). The heat transfer medium (210)leaving the second reactor heat exchanger (HX-2) via the heat transfermedium outlet (216) is at a higher temperature than the heat transfermedium (210) entering the second reactor heat exchanger (HX-2) via theheat transfer medium inlet (212).

The second reactor product gas (222) is discharged from the interior(201) of the second reactor (200) via a second product gas output (224).In embodiments, solids (338), such as ash, molten ash, slag aredischarged from the interior (201) of the second reactor (200) via asolids output (340).

In embodiments, the first reactor (100) may be a cylindrical, up-flow,catalytic, refractory-lined, steel pressure vessel with a fluidized bed.In embodiments, the first reactor (100) may be a cylindrical, up-flow,non-catalytic, refractory-lined, steel pressure vessel with a fluidizedbed. In embodiments, the second reactor (200) may be a cylindrical,down-flow, non-catalytic, refractory-lined, steel pressure vessel. Inembodiments, the second reactor (200) may be rectangular.

In embodiments, a sufficient amount of oxygen-containing gas (218) isprovided to a burner (246) of the second reactor (200) so that excessoxygen-containing gas (218) remains unreacted and exits the burner (246)and thus is also available to react the separated char (144) and/or thechar-depleted product gas (126). In embodiments, the separated char(144) may either be the primary or secondary fuel that reacts with theoxygen-containing gas (118). Herein, the oxygen-containing gas (218) maybe staged and the flow streams swirled as necessary to manage themixing, stoichiometry, flame length, and temperature.

Oxidation or combustion, or partial oxidation, of a source of fuel (240)occurs within the burner (246) where the fuel (240) is reacted with theoxygen-containing gas (218) to generate a combustion stream (250). Inembodiments, the oxygen-containing gas (218) is introduced to the burner(246) in superstoichiometric amounts in proportion and relative to thefuel (240) so as to substantially, completely combust the fuel (240) togenerate carbon dioxide and heat along with an unreacted amount ofoxygen-containing gas (218). In embodiments, a superstoichiometricamount of oxygen is provided to the burner (246) so that when all of thefuel (240) is burned, there is still excess oxygen-containing gas (218)left over. In embodiments, the combustion stream (250) exits the burner(246) in substoichiometric amounts in proportion and relative to thechar (144) and/or the char-depleted product gas so as to substantially,completely react the char and/or the low molecular weight hydrocarbons,volatile organic compounds, semi-volatile organic compounds presentwithin the char-depleted product gas to produce carbon monoxide.

In embodiments, the fuel (240) may be tail-gas from a downstreamreactor, Fischer Tropsch tail-gas, natural gas, propane, amethane-containing gas, naphtha, conditioned syngas, product gas,off-gas from a downstream reactor, or even landfill gas including acomplex mix of different gases created by the action of microorganismswithin a landfill. The char-depleted product gas (126) is reacted withthe combustion stream (250) exiting the burner (246) to produceadditional carbon monoxide and hydrogen.

In embodiments, the burner (246) is an annulus type burner employed toreact the fuel (240) with the oxygen-containing gas (218) through thethermochemical process of combustion. In embodiments, the burner (246)is a multi-orifice, co-annular, burner provided with an arrangement ofseveral passages coaxial with the longitudinal axis of the burner.Multi-orifice burners comprising arrangements of annular concentricchannels for reacting the oxygen-containing gas (218) with the fuel(240) may, in some instances, have a reduced area to permit a highvelocity stream to take place and result in very rapid and completereaction of the combustion stream (250) with the separated char (144)and/or the char-depleted product gas (126) to produce additional carbonmonoxide. The design of the burner (246) is not particularly relevant inFIG. 2. Various types of burners may be used as disclosed in FIGS. 3 to8. Preferably, a burner (246) is selected that is configured to reacteither a combustible fuel (240) or separated char (144) or a mixturethereof with an oxygen-containing gas (218) via combustion reaction toproduce an intensely hot combustion stream (250) comprising carbondioxide, oxygen, and heat. The burner may be equipped with an ignitor.

FIG. 2 shows the burner (246) is that of an annulus type. Inembodiments, the burner (246) may be of the type configured to acceptthe fuel (240) and the oxygen-containing gas (218) through concentricports, wherein the oxygen-containing gas (218) is injected into anannular port (245), and the fuel (240) is injected to the central port(247). The burner (246) ensures rapid and intimate mixing and combustionof the fuel (240) with the oxygen-containing gas (218). The fuel (240)and the oxygen-containing gas (218) are introduced under pressure andcombustion of the fuel (240) is completed in the burner (246) andterminates at the burner nozzle (255). In embodiments, the burner (246)is constructed such that the reaction between the fuel (240) and theoxygen-containing gas (218) takes place entirely outside the burner(246) and only at the burner nozzle (247) so as to provide protection ofthe burner (246) from overheating and from direct oxidation. Inembodiments, the burner (246) or the burner nozzle (247) is equippedwith a cooling water circuit (260) which circulates a source of coolingwater (261) within a portion of the burner (246).

In embodiments, the burner nozzle (247) may be defined by a restrictionconstituting a reduction in area to provide an increase in velocity ofthe combustion stream (250) exiting the burner nozzle (247). Therestriction may even be in some instances a baffle or an impingementplate on which the flame of the combustion stream is stabilized. Theburner nozzle (247) may have a restricting or constricting throat zone,or orifice to accelerate velocity of the combustion stream (250) in thetransition from the combustion zone to the interior (201) of the secondreactor (200) where reaction of the combustion stream (250) and theseparated char (144) and/or the char-depleted product gas (126) takesplace. A restriction, orifice, baffle, or impingement surface isadvantageous to shield the combustion occurring within the burner (246)from pressure fluctuations within the interior (201) of the secondreactor (200) to mediate operational difficulties such as burneroscillation, flash-back, detonation, and blow-out.

In embodiments, combustion stream (250) exiting the burner nozzle (247)may be transferred at velocities within the range of 200 feet per minute(ft/m) to the speed of sound under the existing conditions. Butadvantageously the combustion stream (250) that is discharged from theburner (246), via the burner nozzle (247), is at a velocity between 50and 500 feet per second (ft/s) and typically less than 300 ft/s.

The separated char (144) and/or the char-depleted product gas (126)introduced to the interior (201) of the second reactor (200) which comeinto contact with the combustion stream (250) must not be allowed toremain at high temperatures for more than a fraction of a second, ormore than a few seconds, the critical reaction period limits being about0.1 second to about 10 seconds. Normally it is advantageous to maintainreaction time between the separated char (144) and/or the char-depletedproduct gas (126) and the combustion stream (250) of 1 to 6 seconds tosufficiently completely react the low molecular weight hydrocarbons,SVOC, VOC, and char into additional hydrogen and carbon monoxide andproducts of combustion. Preferably the residence time of the separatedchar (144) and/or the char-depleted product gas (126) and the combustionstream (250) in the reaction zone is about 4 seconds.

The combustion stream (250) discharged from burner (246) is comprised ofan intensely hot mixture of carbon dioxide and excess oxygen-containinggas. The heat generated between the combustion of the fuel (240) withthe oxygen-containing gas (218) in turn elevates the temperature of theexcess unreacted oxygen-containing gas (218) contained within thecombustion stream (250) to a temperature up to 1,500° C. (2,732° F.). Itis preferred to operate the burner (246) at about 1,300° C. (2,372° F.).In embodiments, the combustion stream (250) exiting the burner (246)operates at a temperature ranging from about 1,000° C. (1,832° F.) to1,700° C. (3,092° F.). In embodiments, a nozzle (255) comprising abaffle or impingement plate might be installed to shield the burner(246) from the interior (201) of the second reactor (200).

In embodiments, the burner (246) is a Helmholtz pulse combustionresonator (as disclosed in FIGS. 7 and 8). An oxygen-containing gas(218) and a hydrocarbon (240) may be introduced into the burner (246) toproduce the combustion stream (250) via a pulse combustion reaction.Thus, the burner (246) may comprise an aerodynamic valve or fluidicdiode, combustion chamber and tailpipe or tailpipes. This pulse burner(246) will typically operate in a cyclic fashion comprising the steps offuel and oxygen-containing gas intake or recharge, compression, ignitionand expansion. An ignition or spark source detonates the explosivemixture during start-up. The pulsating flow generated in this burner ischaracterized by a pressure anti-node in the combustion chamber and avelocity anti-node at the exit of the tailpipe. This results incombustion chamber pressure varying from a low (below mean) to a high(above mean) and this aids in drawing in fuel and oxygen-containing gasduring recharge and in pushing out the combustion products through thetailpipe(s) during expansion. The flow exiting the tailpipe ischaracterized by a high velocity pulsating flow which facilitates goodmixing of the exiting oxygen-rich products and the separated char (144)and/or char-depleted product gas (126). Once the first cycle isinitiated, operation is thereafter self-sustaining or self-aspirating.

A pulse combustor burner (246) used herein, and as noted above, is basedon a Helmholtz configuration with an aerodynamic valve. The pressurefluctuations, which are combustion-induced in the Helmholtzresonator-shaped combustion burner (246), coupled with the fluidicdiodicity of the aerodynamic valve burner (246) and nozzle (247), causea biased flow of the combustion stream (250) from the burner (246),through the nozzle (247) and into the interior (201) of the secondreactor (200). This results in the oxygen-containing gas (218) beingself-aspirated by the burner (246) and for an average pressure boost todevelop in the burner (246) to expel the products of combustion at ahigh average flow velocity (typically over 300 ft/s) into and throughthe nozzle (247).

The production of an intense acoustic wave is an inherent characteristicof pulse combustion. Sound intensity in the combustion chamber of burner(246) is normally in the range of 150-190 dB. The operating frequencymay range from 40 to 250 Hz and more typically between 50 and 150 Hz.

FIG. 2 shows one non-limiting representation of a burner (246) includinga central port (247) and an annular port (245), wherein a secondoxygen-containing gas (218) is introduced to the central port (247), anda fuel (240) is introduced to the annular port (245). In embodiments,the fuel (240) introduced to the burner (246) may be tail-gas from adownstream reactor, Fischer Tropsch tail-gas, natural gas, propane, amethane-containing gas, naphtha, conditioned syngas, product gas,off-gas from a downstream reactor, or even landfill gas including acomplex mix of different gases created by the action of microorganismswithin a landfill. FIGS. 3 to 8 show other non-limiting representationsof the burner (246) which is integrated with the second reactor (200).

FIG. 2A:

FIG. 2A shows a simplistic diagram of another embodiment of a productgas production system (1000) including: a first reactor (100) configuredto produce a first product gas (122) including char, a first solidsseparation device (150) configured to separate the char from the firstproduct gas (122) to produce separated char (144) and a firstchar-depleted product gas (126), a second solids separation device(150′) configured to separate additional char from the firstchar-depleted product gas (126) to produce additional separated char(144′) and a second char-depleted product gas (126′), and a secondreactor (200) configured to separately accept both streams of separatedchar (144, 144′) and the second char-depleted product gas (126′),wherein both streams of separated char (144, 144′) are introduced to thesecond reactor (200) at two first elevations (EL1, ELF) and the secondchar-depleted product gas (126′) is also introduced at a secondelevation (EL2), wherein both of the first elevations (EL1, ELF) arelocated higher than the second elevation (EL2) along a vertical axis(AX2) of the second reactor (200).

In embodiments, the solids separation device may comprise a plurality ofserially connected elements, each configured to separate char fromproduct gas. FIG. 2A shows an embodiment (embodiment 2) in whichserially connected cyclones (150, 150′) are each shown to remove char(144, 144′). The char (144,144′) is then introduced into the secondreactor (200) via distinct first and second char inputs (204, 204′), thefirst char input (204) being at a first char elevation (EL1) which ishigher than a second char elevation (EL2) of the second char input(204′). However, both char inputs (204, 204′) are at a higher elevationthan the product gas input (206). While the embodiment seen in FIG. 2Ashows a solid separation device comprising two cyclones), it isunderstood that more than two cyclones (or other elements) may beserially connected.

In the embodiment of FIG. 2A a first product gas (122) is dischargedfrom the first reactor (100) via the first product gas output (124). Thefirst product gas (122) is introduced to the first solids separationdevice (150) to produce a first char-depleted product gas (126) and theseparated char (144). The first char-depleted product gas (126) is thenintroduced to the second solids separation device (150′) to produce asecond char-depleted product gas (126′) and additional separated char(144′). The separated char (144) is routed from the char output (154) ofthe first solids separation device (150) to a first char input (204) ofthe second reactor (100) at a first elevation (EL1). The additionalseparated char (144′) is routed from the char output (154′) of thesecond solids separation device (150′) to a second char input (204′) ofthe second reactor (100) at another first elevation (EL1′).

Char (144) is separated from the first product gas (122) in the firstsolids separation device (150) and is mixed with motive fluid (149) andtransported to the first char input (204) of the second reactor (100).The circle with the “X” in the center illustrates a continuous streamtransferring the char (144) and the motive fluid (149) to the first charinput (204) of the second reactor (100). The additional char (144′) isseparated from the char-depleted product gas (126) in the second solidsseparation device (150′) and is mixed with a motive fluid (149′) andtransported to the second char input (204′) of the second reactor (100).FIGS. 2 and 2A both show the motive fluid (149, 149′) transferred fromFIG. 9 as recycled carbon dioxide, however, a gas, nitrogen, tail-gasfrom a downstream reactor, conditioned syngas, syngas, off-gas from adownstream reactor, steam, superheated steam, a vapor, and a superheatedvapor may also be used.

In embodiments, an eductor (148) is used to mix and transport the motivefluid (149) with the separated char (144) to be transferred to the charinput (204) of the second reactor (200). In embodiments, the eductor(148) may include a venturi eductor and/or a venturi transport systemfor dilute phase pneumatic conveying of the char (144) into the secondreactor (200) with the motive fluid (148). In embodiments, the eductor(148) includes a Solids Handling Eductors provided by Schutte & Koertinglocated at 2510 Metropolitan Drive, Trevose, Pa. 19053 (www.s-k.com). Inembodiments, a first eductor (148) is used to mix and transport themotive fluid (149) with the separated char (144) to be transferred tothe first char input (204) of the second reactor (200). In embodiments,a second eductor (148′) s used to mix and transport the motive fluid(149′) with the additional separated char (144′) to be transferred tothe second char input (204′) of the second reactor (200).

FIG. 3:

FIG. 3 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (3-1), a first annular port (3-2), a second annular port (3-3), anda third annular port (3-4). In embodiments, the first annular port isclosest to the central port (3-1); and the second annular port (3-3) ispositioned in between the first annular port (3-2) and the third annularport (3-4).

Fuel (240) is introduced to the central port (3-1), an oxygen containinggas (218) is introduced to the first annular port (3-2), the separatedchar (144) is introduced to the second annular port (3-3) (via the charinput (204) located at a first elevation (EL1)), additional oxygencontaining gas (218-2) is introduced to the third annular port (3-4).The separated char (144) introduced to the burner (246) of the secondreactor (200) is introduced at a first elevation (EL1), via the charinput (204), located along the vertical axis (AX2) of the second reactor(200). The char-depleted product gas (126) is introduced to the interior(201) of the second reactor (200) at a second elevation (EL2), via aproduct gas input (206), located along the vertical axis (AX2) of thesecond reactor (200), wherein the second elevation (EL2) is locatedbelow the first elevation (EL1).

FIG. 4:

FIG. 4 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (4-1), a first annular port (4-2), and a second annular port (4-3).FIG. 4 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (4-1), a first annular port (4-2), and a second annular port (4-3);wherein the first annular port is closest to the central port (4-1).

The separated char (144) is introduced to the central port (4-1), anoxygen containing gas (218) is introduced to the first annular port(4-2), and additional oxygen containing gas (218-2) is introduced to thesecond annular port (4-3). The separated char (144) introduced to theburner (246) of the second reactor (200) is introduced via the charinput (204), at a first elevation (EL1) located along the vertical axis(AX2) of the second reactor (200). The char-depleted product gas (126)is introduced to the interior (201) of the second reactor (200) via theproduct gas input (206) located at a second elevation (EL2) locatedalong the vertical axis (AX2) of the second reactor (200), wherein thesecond elevation (EL2) is located below the first elevation (EL1).

FIG. 5:

FIG. 5 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (5-1), a first annular port (5-2), and a second annular port (5-3).FIG. 5 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (5-1), a first annular port (5-2), and a second annular port (5-3);wherein the first annular port is closest to the central port (5-1).Fuel (240) is introduced to the central port (5-1), an oxygen containinggas (218) is introduced to the first annular port (5-2), the separatedchar (144) is introduced to the second annular port (5-3).

The separated char (144) introduced to the burner (246) of the secondreactor (200) is introduced via the char input (204) at a firstelevation (EL1) located along the vertical axis (AX2) of the secondreactor (200). The char-depleted product gas (126) is introduced to theinterior (201) of the second reactor (200) via the product gas input(206) at a second elevation (EL2) located along the vertical axis (AX2)of the second reactor (200), wherein the second elevation (EL2) islocated below the first elevation (EL1). In embodiments, an additionaloxygen-containing gas (218-2) may either be introduced coaxially to thechar-depleted product gas (126) or separately at a third elevation (EL3)in between the first elevation (EL1) and the second elevation (EL2). Inembodiments, the additional oxygen-containing gas (218-2) is introducedinto the second reactor (200) to promote partial oxidation of thechar-depleted product gas.

FIG. 6:

FIG. 6 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes: a centralport (6-1) and a first annular port (6-2). The separated char (144) isintroduced to the central port (6-1) and an oxygen containing gas (218)is introduced to the first annular port (6-2).

The separated char (144) introduced to the burner (246) of the secondreactor (200) is introduced via the char input (204) at a firstelevation (EL1) located along the vertical axis (AX2) of the secondreactor (200). The char-depleted product gas (126) is introduced to theinterior (201) of the second reactor (200) at a second elevation (EL2)located along the vertical axis (AX2) of the second reactor (200), viathe product gas input (206) wherein the second elevation (EL2) islocated below the first elevation (EL1).

In embodiments, an additional oxygen-containing gas (218-2) may eitherbe introduced coaxially to the char-depleted product gas (126) orseparately at a third elevation (EL3) in between the first elevation(EL1) and the second elevation (EL2). In embodiments, the additionaloxygen-containing gas (218-2) is introduced into the second reactor(200) to promote partial oxidation of the char-depleted product gas.

FIG. 7:

FIG. 7 shows a simplistic representation of a burner (246) connected tothe second reactor (200), wherein the burner (246) includes a pulsecombustor. FIG. 7 shows the burner (246) as a pulse combustor. The pulsecombustion burner (246) includes: an inlet section (290), a combustionsection (292), and a resonance section (294). FIG. 7 shows the inletsection (290) configured to accept both an oxygen-containing gas (218)and a fuel (240). The oxygen-containing gas (218) and a fuel (240) aremixed and then combusted in the combustion section (292) to produce acombustion stream (250).

The separated char (144) is introduced to the interior (201) of thesecond reactor (200) via a char input (204) located at a first elevation(EL1) located along the vertical axis (AX2) of the second reactor (200).The separated char (144) introduced at the first elevation (EL1) firstreacts with the combustion stream (250) which contains oxygen tosubstantially convert the separated char (144) into carbon monoxide andcarbon dioxide.

The char-depleted product gas (126) is introduced to the interior (201)of the second reactor (200) via the product gas input (206) located atthe second elevation (EL2), lower than the first elevation (EL2), thenreacts with the products of the separated char (144) and combustionstream (250) to substantially convert the low molecular weighthydrocarbons, volatile organic compounds, semi-volatile organiccompounds within the char-depleted product gas (126) into carbonmonoxide and hydrogen. In embodiments, an additional oxygen-containinggas (218-2) may either be introduced coaxially to the char-depletedproduct gas (126) or separately at a third elevation (EL3) in betweenthe first elevation (EL1) and the second elevation (EL2) to achieve andmaintain the desired operating temperature and conversion. Inembodiments, the additional oxygen-containing gas (218-2) is introducedinto the second reactor (200) to promote partial oxidation of thechar-depleted product gas.

FIG. 8:

FIG. 8 shows another simplistic representation of a burner (246)connected to the second reactor (200), wherein the burner (246) includesa pulse combustor. FIG. 8 shows the burner (246) as a pulse combustor.The pulse combustion burner (246) includes: an inlet section (290), acombustion section (292), and a resonance section (294). FIG. 8 showsthe inlet section (290) configured to accept both an oxygen-containinggas (218) and separated char (144), wherein the separated char (144) isintroduced to the burner (246) at a first elevation (EL1) located alongthe vertical axis (AX2) of the second reactor (200). Theoxygen-containing gas (218) and the separated char (144) are mixed andthen combusted in the combustion section (292) to produce a combustionstream (250).

The separated char (144) introduced via the char input (204) located atthe first elevation (EL1) first reacts with the oxygen-containing gas(218) to form the combustion stream (250). The char-depleted product gas(126) introduced via the product gas input (206) located at the secondelevation (EL2), lower than the first elevation (EL2), then reacts withthe combustion stream (250) to substantially convert the low molecularweight hydrocarbons, volatile organic compounds, semi-volatile organiccompounds within the char-depleted product gas (126) into carbonmonoxide and hydrogen. In embodiments, an additional oxygen-containinggas (218-2) may either be introduced coaxially to the char-depletedproduct gas (126) or separately at a third elevation (EL3) in betweenthe first elevation (EL1) and the second elevation (EL2) to achieve andmaintain the desired operating temperature and conversion.

FIG. 9:

FIG. 9 shows a simplistic diagram of one embodiment of IntegratedBiorefinery (IBR) including the product gas production system (1000) asdisclosed in FIGS. 1, 2, and 2A. In embodiments, the product gasproduction system (1000) as disclosed in FIGS. 1, 2, and 2A is includedwithin an Integrated Biorefinery (IBR) for the conversion of acarbonaceous material (102) into a useful product (1500).

In embodiments, the Integrated Biorefinery (IBR) includes a feedstockpreparation system (25), a feedstock delivery system (50), the productgas generation system (1000), a primary gas clean-up system (300), acompression system (400), a secondary gas clean-up system (500), aproduction system (600), and a purification system (700).

In embodiments, the feedstock preparation system (25) is configured toaccept a carbonaceous material via an input (25-1) and discharge acarbonaceous material via an output (25-2). In embodiments, thefeedstock preparation system (25) processes the carbonaceous material inat least one processing step, including one or more processing stepsselected from the group consisting of large objects removal, recyclablesremoval, ferrous metal removal, size reduction, drying or water removal,biowaste removal, non-ferrous metal removal, polyvinyl chloride removal,glass removal, size reduction, and pathogen removal.

In embodiments, the feedstock delivery system (50) is configured toaccept, via an input (50-1), a carbonaceous material from the output(25-2) of the feedstock preparation system (25) and transfer thecarbonaceous material to the input (104) of the first reactor (100)within the product gas production system (1000). In embodiments, thefeedstock delivery system (50) is configured to transfer thecarbonaceous material to interior of the pressurized first reactor andto form a seal between a pressurized interior (101) of the first reactor(100) and the input (50-1) of the feedstock delivery system (50). Inembodiments, the feedstock delivery system (50) includes a plug feedersystem configured to create plugs from the carbonaceous material,wherein the plugs are used to form a seal between a pressurized interior(101) of the first reactor (100). In embodiments, the feedstock deliverysystem (50) includes a densification system configured to create densifythe carbonaceous material and form densified carbonaceous material,wherein the densified carbonaceous material is used to form a sealbetween a pressurized interior (101) of the first reactor (100). Inembodiments, the feedstock delivery system (50) includes a screw augerconfigured to transport the carbonaceous material to the interior (101)of the first reactor (100). In embodiments, the feedstock deliverysystem (50) includes a solids transport conduit configured to transportsolid carbonaceous material to the interior (101) of the first reactor(100). In embodiments, the feedstock delivery system (50) includes alock-hopper configured to transport the carbonaceous material to theinterior (101) of the first reactor (100). The carbonaceous material isdischarged from the output (50-2) of the feedstock delivery system (50)and into the interior (101) of the first reactor (100) via an input(104).

In embodiments, the feedstock delivery system (50) is also configured toaccept a recycle gas (104-0), such as carbon dioxide, discharged from arecycled gas output (500-3) of a downstream secondary gas clean-upsystem (500). In embodiments, the recycle gas (104-0) includes carbondioxide and is removed from product gas in a downstream secondary gasclean-up system (500).

As disclosed in FIG. 9 (and in FIGS. 1 and 2), the product gasproduction system (1000) includes a first reactor (100), a solidsseparation device (150), and a second reactor (200). The first reactor(100) generates a first product gas (122) by reacting a source ofcarbonaceous material (102) with a reactant (106), such as superheatedsteam, in a steam reforming reaction, wherein the first product gas(122) includes syngas comprising hydrogen, carbon monoxide, carbondioxide, low molecular weight hydrocarbons, volatile organic compounds,semi-volatile organic compounds, and char. The first product gas (122)is discharged from the first reactor (100) via a first product gasoutput (124) and is routed towards a solids separation device (150)which separates the char (144) from the first product gas (122) toproduce separated char (144) and char-depleted product gas (126). Thechar-depleted product gas (126) has a reduced amount of char (144)within it relative to the first product gas (122).

In embodiments, the first reactor (100) is also configured to accept arecycle gas (104-1), such as carbon dioxide, discharged from a recycledgas output (500-3) of a downstream secondary gas clean-up system (500).In embodiments, the recycle gas (104-1) may be used for instrumentationpurges for level and/or density measurement devices.

The solids separation device (150) accepts the first product gas (122)via a first separation input (152). The solids separation device (150)accepts the first product gas (122) from the first product gas output(124) of the first reactor (100). The char-depleted product gas (126) isdischarged from the solids separation device (150) via the firstseparation gas output (156). The separated char (144) is discharged fromthe solids separation device (150) via the first separation char output(154).

The second reactor (200) is configured to accept both the separated char(144) and the char-depleted product gas (126) discharged from the solidsseparation device (150). The separated char (144) is introduced to theinterior (201) of the second reactor (200) via a char input (204). Thechar-depleted product gas (126) is introduced to the interior (201) ofthe second reactor (200) via a product gas input (206).

In embodiments, the second reactor (200) is also configured to accept arecycle gas (104-2), such as carbon dioxide, discharged from a recycledgas output (500-3) of a downstream secondary gas clean-up system (500).In embodiments, the recycle gas (104-2) may be used for instrumentationpurges for level and/or density measurement devices, and also may beused to a motive fluid (149) which can be mixed with the separated char(144) for transporting the separated char (144) to the char input (204)of the second reactor (200) (as seen in FIGS. 2 and 2A).

The separated char (144) and the char-depleted product gas (126) areboth reacted within the interior (201) of the second reactor (200) toproduce a second reactor product gas (222). The second reactor productgas (222) is discharged from the second reactor (200) via a secondproduct gas output (224).

In embodiments, the primary gas clean-up system (300) is configured toaccept, via an input (300-1), the second reactor product gas (222)discharged from the second reactor (200) via a second product gas output(224). In embodiments, the primary gas clean-up system (300) isconfigured cool and remove solids and water vapor from the secondreactor product gas (222) and produce a first cleaned product gas whichis discharged via an output (300-2).

In embodiments, the compression system (400) is configured to accept,via an input (400-1), the first cleaned product gas via the output(300-2) of the primary gas clean-up system (300) and compress the firstcleaned product gas to produce a compressed product gas. The compressedproduct gas is discharged from an output (400-2) of the compressionsystem (400) and is routed to the input (500-1) of the secondary gasclean-up system (500). The compression system (400) is configured toincrease a pressure of the first cleaned product and discharge thecompressed product gas via the output (400-2) at a second pressuregreater than a first pressure at which the first cleaned product gasentered via the compression system input (400-1).

In embodiments, the secondary gas clean-up system (500) is configured toaccept the compressed product gas from the output (400-2) of thecompression system (400) and produce a second cleaned product gas thatis discharged from an output (500-2) of the secondary gas clean-upsystem (500). In embodiments, the secondary gas clean-up system (500) isconfigured to remove carbon dioxide from at least a portion of thecompressed product gas discharged from the compression system (400) witha carbon dioxide removal system to produce from a recycled gas output(500-3) which may then be used as a recycle gas, or a carbondioxide-rich stream, in the feedstock delivery system (50) (as recyclegas (104-0)), the first reactor (100) (as recycle gas (104-1)), or to bemixed with the separated char (144) transferred to the second reactor(200) (as the recycle gas (104-2) which may be used as the motive fluid(149) for transferring the separated char (144) from the solidsseparation device (150) to the char input (204) of the second reactor(200) as seen in FIGS. 2 and 2A).

In embodiments, the secondary gas clean-up system (500) removes carbondioxide from the compressed product gas using a carbon dioxide removalsystem. In embodiments, the carbon dioxide removal system within thesecondary gas clean-up system (500) includes one or more systemsselected from the group consisting of a membrane, solvent-basedscrubbing systems using amines or physical solvents (i.e., Rectisol,Selexol, Sulfinol), a wet limestone scrubbing system, a spray dryscrubber, a clause processing system, a solvent based sulfur removalprocesses such as the UC Sulfur Recovery Process (UCSRP), a hightemperature sorbent, glycol ether, diethylene glycol methyl ether (DGM),a regenerable sorbent, a non-regenerable sorbent, molecular sievezeolites, calcium based sorbents, FeO, MgO or ZnO-based sorbents orcatalysts, iron sponge, potassium-hydroxide-impregnated activated-carbonsystems, impregnated activated alumina, titanium dioxide catalysts,vanadium pentoxide catalysts, tungsten trioxide catalysts, sulfurbacteria (Thiobacilli), sodium biphospahte solutions, aqueous ferriciron chelate solutions, potassium carbonate solutions, alkali earthmetal chlorides, magnesium chloride, barium chloride, crystallizationsystems, bio-catalyzed scrubbing processes such as the THIOPAQ Scrubber,and hydrodesulphurization catalysts.

In embodiments, the secondary gas clean-up system (500) is alsoconfigured to remove contaminants from product gas, wherein thecontaminants include ammonia (which can be removed via absorption and/oradsorption), VOCs (which can be removed via adsorption), sulfur (whichcan be removed via absorption and/or adsorption), carbonyl sulfide(which can be removed via hydrolysis), metals (which can be removed viaabsorption and/or adsorption), hydrogen purification (purified withadsorption and/or a membrane).

In embodiments, the production system (600) is configured to accept, viaan input (600-1), and produce an intermediate product from at least aportion of the second cleaned product gas discharged from the output(500-2) of the secondary gas clean-up system (500). In embodiments, theproduction system (600) produces and discharges an intermediate productvia an output (600-2) which is routed to the input (700-1) of apurification system (700). In embodiments, the production system (600)also produces and discharges a gaseous composition, or a tail-gas, via arecycle output (600-3) which is routed to the first reactor heatexchanger (HX-1) (as seen in FIGS. 2 and 2A), or to the burner (246) asshown in FIGS. 2 to 9 for use as the source of fuel (240). Inembodiments, the production system (600) produces and discharges agaseous composition, or the tail-gas, via a recycle output (600-3) whichmay be used as the motive fluid (149) and mixed with the separated char(144) to be transferred to the char input (204) of the second reactor(200).

In embodiments, the intermediate product produced in the productionsystem (600) includes one or more systems selected from the groupconsisting of ethanol, mixed alcohols, methanol, dimethyl ether,chemicals or chemical intermediates (plastics, solvents, adhesives,fatty acids, acetic acid, carbon black, olefins, oxochemicals, ammonia,etc.), Fischer-Tropsch products (LPG, Naphtha, Kerosene/diesel,lubricants, waxes), synthetic natural gas. In embodiments, theproduction system (600) includes one or more production systems selectedfrom the group consisting of a reactor, a methanation reactor, a multitubular reactor, a multi tubular fixed-bed reactor, an entrained flowreactor, a slurry reactor, a fluid-bed reactor, a circulating catalystreactor, a riser reactor, a can reactor, a microchannel reactor, a fixedbed reactor, a bioreactor, and a moving bed reactor.

In embodiments, the production system (600) includes a cobalt catalystand/or an iron catalyst. In embodiments, the production system (600)includes a methanation reactor to produce synthetic natural gas from thesecond cleaned product gas. In embodiments, the production system (600)includes a catalyst and can produce liquid fuels such as mixed alcohols(e.g., a mixture of both ethanol and methanol), dimethyl ether,Fischer-Tropsch products, or the like. In embodiments, the productionsystem (600) includes a bioreactor containing microorganisms. Themicroorganisms produce a liquid fuel (e.g., ethanol, 1-butanol,2-butanol) and/or chemicals within the bioreactor.

In embodiments, the intermediate product includes a liquid fuel and/or achemical that is produced in a bioreactor is then distilled in thepurification system (700). In embodiments, the liquid fuel and/or achemical produced in the bioreactor is then removed using a membrane. Inembodiments, the liquid fuel and/or a chemical produced in thebioreactor is then dehydrated using pressure swing adsorption. Inembodiments, the liquid fuel and/or a chemical produced in thebioreactor is then dehydrated using an adsorbent. In embodiments, theliquid fuel and/or a chemical produced in the bioreactor is thendehydrated using 3 angstrom molecular sieves.

In embodiments, the intermediate product includes a chemical produced inthe bioreactor includes one or more selected from the group consistingof: 3-hydroxypropionate; mevalonate; mevalonic acid; isoprene;aromatics; benzoate (p-hydroxyl, 2-amino, dihydroxy); salicylate;1-propanol; 1,2-propanediol; (R)-1,2-propanediol; (S)-1,2-propanediol;mixed isomers of 1,2-propanediol; acetoin; methyl ethyl ketone;branched-chain amino acids; valine, leucine, isoleucine; succinate;lactate; 2,3-butanediol; (R,R)-2,3-butanediol; meso-2,3-butanediol;mixed isomers of 2,3-butanediol; citramalate; 1,3-butanediol;(R)-1,3-butanediol; (S)-1,3-butanediol; mixed isomers of 1,3-butanediol;3-hydroxybutyrate; (R)-3-hydroxybutyrate; (S)-3-hydroxybutyrate; mixedisomers of 3-hydroxybutyrate; butyrate; acetone; isopropanol; acetate;1,3-butadiene; biopolymers; isobutene; long chain alcohols.

In embodiments, when ethanol is produced in the bioreactor of theproduction system (600), it is then distilled in the purification system(700). In embodiments, the ethanol produced in the bioreactor is thenremoved using a membrane. In embodiments, the ethanol produced in thebioreactor is then dehydrated using pressure swing adsorption. Inembodiments, the ethanol produced in the bioreactor is then dehydratedusing an adsorbent. In embodiments, the ethanol produced in thebioreactor is then dehydrated using 3 angstrom molecular sieves.

In embodiments, the bioreactor includes one or more type of bioreactorsselected from the group consisting of a continuous stirred tankbioreactor, a bubble column bioreactor, a microbubble reactor, anairlift bioreactor, a fluidized bed bioreactor, a packed bed bioreactor,and a photo-bioreactor. In embodiments, the microorganisms used withinthe bioreactor include genetically modified organisms. In embodiments,the microorganisms used within the bioreactor do not include geneticallymodified organisms. In embodiments, the microorganisms used within thebioreactor include gas fermenting organisms. In embodiments, themicroorganisms used within the bioreactor undergo anaerobic respiration.In embodiments, the microorganisms used within the bioreactor undergofermentation. In embodiments, the microorganisms used within thebioreactor include anaerobic bacteria. In embodiments, the bioreactorincludes a liquid nutrient medium used for culturing the microorganismsand the ethanol is produced within the bioreactor by the microorganismswhich secrete ethanol which accumulates within the liquid nutrientmedium.

In embodiments, the purification system (700) is configured to acceptthe intermediate product produced and discharged from the productionsystem (600) via the output (600-2). A purified product (1500) isdischarged from an output (700-2) of the purification system (700). Inembodiments, the purification system (700) produces and discharges agaseous composition, or off-gas stream, via a recycle output (700-3)which is routed to the first reactor heat exchanger (HX-1) (as seen inFIGS. 2 and 2A), or to the burner (246) as shown in FIGS. 2 to 9 for useas the source of fuel (240). In embodiments, the purification system(700) upgrades the intermediate product. In embodiments, thepurification system (700) produces and discharges a gaseous composition,or the off-gas stream, via a recycle output (700-3) which may be used asthe motive fluid (149) and mixed with the separated char (144) to betransferred to the char input (204) of the second reactor (200). Inembodiments, if isomerization, hydrotreating, hydrocracking,distillation, and adsorption are used, the off-gas includes hydrogen orhydrocarbons. In embodiments, if synthetic natural gas is produced andadsorption is used the off-gas includes hydrogen or hydrocarbons.

In embodiments, the purification system (700) hydrotreats theintermediate product produced and discharged from the production system(600). In embodiments, the purification system (700) hydrocracks theintermediate product produced and discharged from the production system(600). In embodiments, the purification system (700) distills theintermediate product produced and discharged from the production system(600). In embodiments, the purification system (700) adsorbs impuritiesfrom the intermediate product produced and discharged from theproduction system (600). In embodiments, the purification system (700)accepts the intermediate product from the output (600-2) of theproduction system (600) and purifies with one or more processing stepsselected from the group consisting of isomerization, hydrotreating,hydrocracking, distillation, and adsorption.

It will be appreciated that the foregoing examples, given for purposesof illustration, are not to be construed as limiting the scope of thisdisclosure. Although only a few exemplary embodiments of this disclosurehave been described in detail above, those skilled in the art willreadily appreciate that many variation of the theme are possible in theexemplary embodiments without materially departing from the novelteachings and advantages of this disclosure. Accordingly, all suchmodifications are intended to be included within the scope of thisdisclosure that is defined in the following claims and all equivalentsthereto. Further, it is recognized that many embodiments may beconceived in the design of a given system that do not achieve all of theadvantages of some embodiments, yet the absence of a particularadvantage shall not be construed to necessarily mean that such anembodiment is outside the scope of the present disclosure.

Thus, specific systems and methods of a two-stage syngas productionsystem integrated within an Integrated Biorefinery (IBR) have beendisclosed. It should be apparent, however, to those skilled in the artthat many more modifications besides those already described arepossible without departing from the inventive concepts herein. Theinventive subject matter, therefore, is not to be restricted except inthe spirit of the disclosure. Moreover, in interpreting the disclosure,all terms should be interpreted in the broadest possible mannerconsistent with the context. In particular, the terms “comprises” and“comprising” should be interpreted as referring to elements, components,or steps in a non-exclusive manner, indicating that the referencedelements, components, or steps may be present, or utilized, or combinedwith other elements, components, or steps that are not expresslyreferenced.

Although the foregoing text sets forth a detailed description ofnumerous different embodiments of the disclosure, it should beunderstood that the scope of the disclosure is defined by the words ofthe claims set forth at the end of this patent. The detailed descriptionis to be construed as exemplary only and does not describe everypossible embodiment of the disclosure because describing every possibleembodiment would be impractical, if not impossible. Numerous alternativeembodiments could be implemented, using either current technology ortechnology developed after the filing date of this patent, which wouldstill fall within the scope of the claims defining the disclosure.

Thus, many modifications and variations may be made in the techniquesand structures described and illustrated herein without departing fromthe spirit and scope of the present disclosure. Accordingly, it shouldbe understood that the methods and apparatus described herein areillustrative only and are not limiting upon the scope of the disclosure.

Unless the context dictates the contrary, all ranges set forth hereinshould be interpreted as being inclusive of their endpoints, andopen-ended ranges should be interpreted to include commerciallypractical values. Similarly, all lists of values should be considered asinclusive of intermediate values unless the context indicates thecontrary.

The recitation of ranges of values herein is merely intended to serve asa shorthand method of referring individually to each separate valuefalling within the range. Unless otherwise indicated herein, eachindividual value is incorporated into the specification as if it wereindividually recited herein. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided with respectto certain embodiments herein is intended merely to better illuminatethe disclosure and does not pose a limitation on the scope of thedisclosure otherwise claimed. No language in the specification should beconstrued as indicating any non-claimed element essential to thepractice of the disclosure.

Groupings of alternative elements or embodiments of the disclosuredisclosed herein are not to be construed as limitations. Each groupmember can be referred to and claimed individually or in any combinationwith other members of the group or other elements found herein. One ormore members of a group can be included in, or deleted from, a group forreasons of convenience and/or patentability. When any such inclusion ordeletion occurs, the specification is herein deemed to contain the groupas modified thus fulfilling the written description of all Markushgroups used in the appended claims.

It should be apparent to those skilled in the art that many moremodifications besides those already described are possible withoutdeparting from the inventive concepts herein. The inventive subjectmatter, therefore, is not to be restricted except in the spirit of theappended claims. Moreover, in interpreting both the specification andthe claims, all terms should be interpreted in the broadest possiblemanner consistent with the context. In particular, the terms “comprises”and “comprising” should be interpreted as referring to elements,components, or steps in a non-exclusive manner, indicating that thereferenced elements, components, or steps may be present, or utilized,or combined with other elements, components, or steps that are notexpressly referenced. Where the specification claims refers to at leastone of something selected from the group consisting of A, B, C . . . andN, the text should be interpreted as requiring only one element from thegroup, not A plus N, or B plus N, etc.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, a limitednumber of the exemplary methods and materials are described herein.

It must be noted that as used herein and in the appended claims, thesingular forms “a”, “an”, and “the” include plural referents unless thecontext clearly dictates otherwise.

LISTING OR REFERENCE NUMERALS

-   product gas production system (1000)-   first reactor (100)-   interior (101)-   first vertical axis (AX1)-   carbonaceous material (102)-   input (104)-   particulate heat transfer material (105)-   reactant (106)-   reactant input (108)-   first fuel (110)-   combustion stream (114)-   first oxygen-containing gas (118)-   first oxygen-containing gas input (120)-   first product gas (122)-   first product gas output (124)-   internal cyclone (125)-   char-depleted product gas (126, 126′)-   char depleted product gas conduit (128, 128′)-   separated char (144, 144′)-   eductor (148, 148′)-   gas (149, 149′)-   solids separation device (150, 150′)-   first separation input (152, 152′)-   first separation char output (154, 154′)-   first separation gas output (156, 156′)-   fluid bed level (L-1)-   fluidization distributor (121)-   freeboard (FB-1)-   first reactor heat exchanger (HX-1)-   first elevation (EL1)-   second elevation (EL2)-   second reactor (200)-   interior (201)-   second vertical axis (AX2)-   char input (204, 204′)-   product gas input (206)-   oxygen-containing gas (218)-   second oxygen-containing gas input (220)-   second product gas output (224)-   second reactor product gas (222)-   fuel (322)-   burner (346)-   central port (347)-   annular port (345)-   burner nozzle (355)-   second reactor heat exchanger (HX-2)-   heat transfer medium outlet (216)-   heat transfer medium inlet (212)-   heat transfer medium (210)-   solids (338)-   solids output (340)-   combustion stream (350)-   inlet section (405)-   combustion section (410)-   tail pipe section (415)-   third elevation (EL3)-   feedstock preparation system (25)-   input (25-1)-   output (25-2)-   feedstock delivery system (50)-   input (50-1)-   output (50-2)-   recycle gas (104-0)-   recycle gas (104-1)-   recycle gas (104-2)-   primary gas clean-up system (300)-   input (300-1)-   output (300-2)-   compression system (400)-   input (400-1)-   output (400-2)-   secondary gas clean-up system (500)-   input (500-1)-   output (500-2)-   recycled gas output (500-3)-   production system (600)-   input (600-1)-   output (600-2)-   recycle-gas (600-3)-   purification system (700)-   input (700-1)-   output (700-2)-   recycle-gas (700-3)

What is claimed is:
 1. A method of producing a final product gas from acarbonaceous material, comprising: in a first reactor, steam reformingthe carbonaceous material to produce a first product gas including char,hydrogen, carbon monoxide, carbon dioxide, and hydrocarbons; in a solidsseparation device external to the first reactor, separating the charfrom the first product gas to produce separated char and char-depletedproduct gas, wherein the char-depleted product gas has a reduced amountof char relative to the first product gas; introducing into a secondreactor, the separated char via a first char input and the char-depletedproduct gas via a product gas input distinct from the first char input;introducing an oxygen-containing gas into the second reactor; and in thesecond reactor, reacting the oxygen-containing gas with the separatedchar and the char-depleted product gas to produce a final product gas,the final product gas having a reduced amount of char and a reducedamount of hydrocarbons, relative to the char-depleted product gas;wherein: along a vertical axis of the second reactor, the separated charis introduced into the second reactor above the char-depleted productgas.
 2. The method according to claim 1, wherein the solids separationdevice comprises serially connected first and second cyclones; and themethod comprises: passing the first product gas through both the firstand second cyclones to produce the char-depleted product gas, with thefirst cyclone producing the separated char and the second cycloneproducing additional char; and introducing, into the second reactor, theseparated char via the first char input and the additional char via asecond char input.
 3. The method according to claim 2, comprising:introducing into the second reactor, both the separated char and theadditional char above the char-depleted product gas, along the verticalaxis.
 4. The method according to claim 1, wherein: the hydrocarbons inthe first product gas include low molecular weight hydrocarbons,aromatic hydrocarbons, and/or polyaromatic hydrocarbons; and the lowmolecular weight hydrocarbons include one or more selected from thegroup consisting of methane, ethane, ethylene, propane, propylene,butane, and butene.
 5. The method according to claim 1, comprising:introducing a fuel to the second reactor; and reacting theoxygen-containing gas with the fuel using a burner in the secondreactor.
 6. The method according to claim 5, wherein: the fuel includesone or more selected from the group consisting of tail-gas,Fischer-Tropsch tail-gas, natural gas, conditioned syngas, propane, amethane-containing gas, naphtha, and off-gas from a liquid fuelupgrading unit.
 7. The method according to claim 1, comprising:entraining the separated char in a motive fluid to produce a char andmotive fluid mixture; and transferring the char and motive fluid mixtureto the second reactor; wherein: the motive fluid comprises one or moreselected from the group consisting of a gas, carbon dioxide, nitrogen,tail-gas, conditioned syngas, syngas, off-gas from a downstream reactor,steam, superheated steam, a vapor, and a superheated vapor.
 8. Themethod according to claim 7, comprising: entraining the separated charin the motive fluid in an eductor to produce the char and motive fluidmixture.
 9. The method according to claim 1, comprising, in the firstreactor: indirectly heating particulate heat transfer material in thefirst reactor with a plurality of pulse combustion heat exchangers; andintroducing superheated steam and the carbonaceous material into thefirst reactor to steam reform the carbonaceous material.
 10. The methodaccording to claim 9, comprising: also introducing an oxygen-containinggas into the first reactor to promote partial oxidation of thecarbonaceous material to produce carbon monoxide and carbon dioxide. 11.The method according to claim 1, wherein: introducing additionaloxygen-containing gas into the second reactor between the first charinput and the product gas input along the vertical axis to promotepartial oxidation of the char-depleted product gas.
 12. A method toproduce a purified product from carbonaceous material, comprising:producing a final product gas from the carbonaceous material accordingto claim 1 after introducing the carbonaceous material into the firstreactor from a feedstock delivery system; in a primary gas clean-upsystem, cooling and removing solids and water vapor from the finalproduct gas to produce a first cleaned product gas; in a compressionsystem, compressing the first cleaned product gas to produce acompressed product gas; in a secondary gas clean-up system, removingcontaminants and carbon dioxide from the compressed product gas toproduce a second cleaned product gas and a carbon dioxide-rich stream;in a production system, producing an intermediate product from at leasta portion of the second cleaned product gas, the intermediate productincludes one or more selected from the group consisting of liquid fuel,a chemical, ethanol, mixed alcohols, methanol, dimethyl ether,Fischer-Tropsch products, and synthetic natural gas; and in apurification system, purifying or upgrading the intermediate product toproduce a purified product, wherein the purification system includes oneor more selected from the group consisting of isomerization,hydrotreating, hydrocracking, distillation, and adsorption.
 13. Themethod according to claim 12, comprising: recycling and mixing at leasta portion of the carbon dioxide-rich stream removed in the secondary gasclean-up system with the char produced in claim 1 to produce a mixtureof char and carbon dioxide, and transferring the mixture of char andcarbon dioxide to the first char input of the second reactor.
 14. Themethod according to claim 12, wherein: in the production system,producing tail gas, and recycling and mixing at least a portion of thetail gas with the char produced in claim 1 to produce a mixture of charand gas, and transferring the mixture of char and tail gas to the firstchar input of the second reactor.
 15. The method according to claim 12,wherein: in the production system, producing tail-gas, and introducingat least a portion of the tail-gas to the second reactor, and reactingthe tail-gas with the oxygen-containing gas prior to reaction with thechar and/or the char-depleted product gas.
 16. The method according toclaim 12, wherein: in the purification system, producing an off-gasstream, and recycling and mixing at least a portion of the off-gasstream with the char produced in claim 1 to produce a mixture of charand gas, and transferring the mixture of mixture of char and gas to thefirst char input of the second reactor; and/or in the purificationsystem, producing off-gas stream, and introducing at least a portion ofthe off-gas stream to the second reactor, and reacting the off-gasstream with the oxygen-containing gas prior to reaction with the charand/or the char-depleted product gas.
 17. The method according to claim12, wherein: the first reactor comprises a cylindrical, up-flow,refractory-lined, steel pressure vessel including a fluidized bed; andthe second reactor comprises a cylindrical, down-flow, non-catalytic,refractory-lined, steel pressure vessel.
 18. The method according toclaim 12, wherein: the carbonaceous material includes municipal solidwaste; and in a feedstock preparation system, processing the municipalsolid waste to produce sorted municipal solid waste in at least oneprocessing step, including one or more processing steps selected fromthe group consisting of large objects removal, recyclables removal,ferrous metal removal, size reduction, drying or water removal, biowasteremoval, non-ferrous metal removal, polyvinyl chloride removal, glassremoval, size reduction and pathogen removal; and introducing the sortedmunicipal solid waste to the feedstock delivery system.
 19. The methodaccording to claim 12, wherein: in the production system, producing theintermediate product from at least a portion of the second cleanedproduct gas within one or more reactors selected from the groupconsisting of a multi-tubular reactor, a multi-tubular fixed-bedreactor, an entrained flow reactor, a slurry reactor, a fluid bedreactor, a circulating catalyst reactor, a riser reactor, a can reactor,a microchannel reactor, a fixed bed reactor, a bioreactor and a movingbed reactor.
 20. The method according to claim 19, wherein: the reactorincludes one or more bioreactors selected from the group consisting of acontinuous stirred tank bioreactor, a bubble column bioreactor, amicrobubble reactor, an airlift bioreactor, a fluidized bed bioreactor,a packed bed bioreactor and a photo-bioreactor.
 21. The method accordingto claim 20, wherein: the bioreactor includes genetically modifiedorganisms which undergo anaerobic respiration.